Synthesis of Photoluminescent 2D Self-Assembled Silver Thiolate Nanoclusters for Sensors and Biomolecule Support.

Silver thiolate nanoclusters (Ag NCs) show distinctive optical properties resulting from their hybrid nature, metallic and molecular, exhibiting size-, structure-, and surface-dependent photoluminescence, thus enabling the exploitation of Ag NCs for potential applications in nanobiotechnology, catalysis, and biomedicine. However, tailoring Ag NCs for specific applications requires achieving long-term stability and may involve modifying surface chemistry, fine-tuning ligand composition, or adding functional groups. In this study, we report the synthesis of novel Ag NCs using 2-ethanephenylthiolate (SR) as a ligand, highlight critical points addressing stability, and characterize their optical and structural properties. A preliminary electrical characterization revealed high anisotropy, well suited for potential use in electronics/sensing applications. We also present the synthesis and characterization of Ag NCs using 10-carboxylic 2-ol thiolate (SR'COOH) having a terminal carboxylic group for conjugation with amine-containing molecules. We present a preliminary assessment of its bioconjugation capability using bovine serum albumin as a model protein indicating its prospective application as a biomolecule support.

Phase Transition and Point Defects in the Ferroelectric Molecular Perovskite (MDABCO)(NH4)I3.

We measured the anelastic, dielectric and structural properties of the metal-free molecular perovskite (ABX3) (MDABCO)(NH4)I3, which has already been demonstrated to become ferroelectric below TC= 448 K. Both the dielectric permittivity measured in air on discs pressed from powder and the complex Young's modulus measured on resonating bars in a vacuum show that the material starts to deteriorate with a loss of mass just above TC, introducing defects and markedly lowering TC. The elastic modulus softens by 50% when heating through the initial TC, contrary to usual ferroelectrics, which are stiffer in the paraelectric phase. This is indicative of improper ferroelectricity, in which the primary order parameter of the transition is not the electric polarization, but the orientational order of the MDABCO molecules. The degraded material presents thermally activated relaxation peaks in the elastic energy loss, whose intensities increase together with the decrease in TC. The peaks are much broader than pure Debye due to the general loss of crystallinity. This is also apparent from X-ray diffraction, but their relaxation times have parameters typical of point defects. It is argued that the major defects should be of the Schottky type, mainly due to the loss of (MDABCO)2+ and I-, leaving charge neutrality, and possibly (NH4)+ vacancies. The focus is on an anelastic relaxation process peaked around 200 K at ∼1 kHz, whose relaxation time follows the Arrhenius law with τ0 ∼ 10-13 s and E≃0.4 eV. This peak is attributed to I vacancies (VX) hopping around MDABCO vacancies (VA), and its intensity presents a peculiar dependence on the temperature and content of defects. The phenomenology is thoroughly discussed in terms of lattice disorder introduced by defects and partition of VX among sites that are far from and close to the cation vacancies. A method is proposed for calculating the relative concentrations of VX, that are untrapped, paired with VA or forming VX-VA-VX complexes.

The Addition of Co into CuO-ZnO Oxides Triggers High Antibacterial Activity and Low Cytotoxicity.

In the present work, a simple two-step method is proposed for mixed oxide synthesis aimed at the achievement of antibacterial nanomaterials. In particular, Cu, Zn and Co have been selected to achieve single-, double- and triple-cation oxides. The synthesized samples are characterized by XRD, IR, SEM and EDX, indicating the formation of either crystalline or amorphous hydrocarbonate precursors. The oxides present one or two crystalline phases, depending on their composition; the triple-cation oxides form a solid solution of tenorite. Also, the morphology of the samples varies with the composition, yielding nanoparticles, filaments and hydrangea-like microaggregates. The antibacterial assays are conducted against E. coli and indicate an enhanced efficacy, especially displayed by the oxide containing 3% Co and 9% Zn incorporated into the CuO lattice. The oxides with the highest antibacterial properties are tested for their cytotoxicity, indicating a low toxicity impact, in line with literature data.

CuO Nanoparticles and Microaggregates: An Experimental and Computational Study of Structure and Electronic Properties.

The link between morphology and properties is well-established in the nanoparticle literature. In this report, we show that different approaches in the synthesis of copper oxide can lead to nanoparticles (NPs) of different size and morphology. The structure and properties of the synthesized NPs are investigated with powder X-ray diffraction, scanning electron microscopy (SEM), and diffuse reflectance spectroscopy (DRS). Through detailed SEM analyses, we were able to correlate the synthetic pathways with the particles' shape and aggregation, pointing out that bare hydrothermal pathways yield mainly spheroidal dandelion-like aggregates, whereas, if surfactants are added, the growth of the nanostructures along a preferential direction is promoted. The effect of the morphology on the electronic properties was evaluated through DRS, which allowed us to obtain the electron bandgap in every system synthesized, and to find that the rearrangement of threaded particles into more compact structures leads to a reduction in the energy difference. The latter result was compared with Density Functional Theory (DFT) computational models of small centrosymmetric CuO clusters, cut from the tenorite crystal structure. The computed UV-Vis absorption spectra obtained from the clusters are in good agreement with experimental findings.

Sustainable Approaches to the Synthesis of Metallophthalocyanines in Solution.

This work aims to investigate more sustainable reaction conditions for the synthesis of metallophthalocyanines. Anisole, glycerol and their mixtures have been investigated as reaction media for the tetramerization of phthalonitriles. Acetates of three divalent first-transition metal cations, Co(II), Cu(II) and Zn(II), were used and several bases were tested, depending on the chosen substrates and reaction conditions, with a view to making the whole process more sustainable while ensuring its scalability. Unsubstituted phthalocyanines were synthesized to analyze the behavior of the different metal ions in terms of reactivity in the new reaction media, resulting in a general Cu > Co > Zn trend, while the nonpolar tetra-tert-butyl substitution was investigated to evaluate the synthesis of soluble derivatives in the new conditions. Furthermore, the potassium hydroxide (KOH)-aided statistical synthesis of the unsymmetrical 9(10), 16(17), 23(24)-tri-tert-butyl-2-iodophthalocyaninato zinc(II), starting from 4-tert-butylphthalonitrile and 4-iodophthalonitrile in a glycerol/anisole mixture, proceeded with a satisfactory 26% yield. Our results provide insights into the investigation of new reaction environments and the understanding of their strengths and weaknesses, with a view to further increasing the sustainability of the synthesis of metallomacrocycles with high added value while lowering their production cost.

Competition between Polar and Antiferrodistortive Modes and Correlated Dynamics of the Methylammonium Molecules in MAPbI3 from Anelastic and Dielectric Measurements.

The mechanisms behind the exceptional photovoltaic properties of the metallorganic perovskites are still debated and include a ferroelectric (FE) state from the ordering of the electric dipoles of the organic molecules. We present the first anelastic (complex Young's modulus) and new dielectric measurements on CH3NH3PbI3, which provide new insight into the reorientation dynamics of the organic molecules and the reason why they do not form a FE state. The permittivity is fitted within the tetragonal phase with an expression that includes the coupling between FE and octahedral tilt modes, indicating that the coupling is competitive and prevents FE ordering. The onset of the orthorhombic phase is accompanied by sharp stiffening, analogous to the drop of permittivity, due to the hindered molecular dynamics. On further cooling, an intense anelastic relaxation process without a dielectric counterpart suggests the reorientation of clusters of molecules with strong antiferroelectric correlations.

Nanocluster superstructures or nanoparticles? The self-consuming scaffold decides.

We show that using the same reaction procedure, by hindering or allowing the formation of a reaction intermediate, the Ag+dodecanethiolate polymeric complex, it is possible to selectively obtain Ag dodecanethiolate nanoparticles or Ag dodecanethiolate nanoclusters in the size range 4-2 nm. Moreover, the Ag dodecanethiolate nanoclusters display a lamellar superstructure templated from the precursor Ag+dodecanethiolate polymeric complex. A plausible formation mechanism is illustrated where, starting from the precursor and scaffold lamellar Ag+ thiolate polymeric complex, first the nanocluster Agn0 core is formed by reduction of isoplanar Ag+ ions, followed by Ag+ thiolate units that build protection, the nanocluster shell, around the core. The nanoclusters are characterized by elemental analyses, XRD, ATR-FTIR, XPS, XAS, MALDI, ESI, UV-Vis and fluorescence measurements. The luminescent Ag15(dodecanethiolate)11·2H2O nanocluster is achieved in good yield after 4 hours of reaction whereas after 2 hours, the luminescent Ag35(dodecanethiolate)16 is isolated. Both Ag nanoclusters present emission bands in the range 330-450 nm, the shifting depending on the excitation wavelength. This phenomenon is attributed to a possible dipolar state causing distribution in energies due to variability of dipole-dipole interactions. Moreover, both nanoclusters further present a NIR emission at about 700 nm independent from the excitation wavelength. Thanks to their optical and structural properties, the synthesized nanoclusters, perfect molecular/nanoparticle hybrids, have great potentiality for new applications in nanotechnologies.

High yield synthesis of pure alkanethiolate-capped silver nanoparticles.

One-phase, one-pot synthesis of Ag(0) nanoparticles capped with alkanethiolate molecules has been optimized to easily achieve a pure product in quantitative yield. We report the synthesis of dodecanethiolate-capped silver particles and the chemophysical, structural, and morphologic characterization performed by way of UV-vis, (1)H NMR, and X-ray photoelectron (XPS) spectroscopies, X-ray powder diffraction (XRD) and X-ray absorption fine structure analysis (XFAS), electron diffraction and high-resolution transmission electron microscopy (HR-TEM), and scanning and transmission electron microscopy (SEM and TEM). Depending on the molar ratio of the reagents (dodecylthiosulphate/Ag(+)), the mean Ag(0) particle size D(XRD) is tuned from 4 to 3 nm with a narrow size distribution. The particles are highly soluble, very stable in organic solvents (hexane, toluene, dichloromethane, etc.), and resistant to oxidation; the hexane solution after one year at room temperature does not show any precipitation or formation of oxidation byproducts.

A novel 1D-AF hybrid organic-inorganic chromium(II) methyl phosphonate dihydrate: synthesis, X-ray crystal and molecular structure, and magnetic properties.

Light-blue crystals of chromium(II) methyl phosphonate dihydrate, [Cr(CH(3)PO(3))(H(2)O)].H(2)O, were obtained in water by mixing filtered solutions of methylphosphonic acid and chromium(II) chloride in the presence of urea in an inert atmosphere. The compound was characterized by elemental analysis, TGA-DSC, X-ray crystallography, magnetic measurements, and UV-visible and FT-IR spectroscopies. The crystal and molecular structures (orthorhombic Pnma (no. 62): a = 4.4714(5) A, b = 6.8762(7) A, c = 19.180(2) A, Z = 4) have been solved using single-crystal X-ray diffraction. The chromium(II) ion is six-coordinated by oxygens (4 + 2) to form an elongated octahedron, with the four equatorial oxygen atoms belonging to [-PO(3)](2-) phosphonate groups. This stereochemistry of the Cr(II) ion (high-spin d(4) electronic configuration) is ascribed to the Jahn-Teller effect. The [CrO(6)] chromophore, the [CH(3)PO(3)](2-) anions, and the water molecules build a novel one-dimensional (1D) metal(II) oxide chain, anchored to each other within the ab plane by two oxygens of the phosphonate ligand. Within the chain, each Cr(2+) ion is connected through double oxygen bridges to its two neighbors, forming edge-sharing octahedra running along the b axis. The chains are further connected with the adjacent chains by phosphonate [-PO(3)](2-) groups of the ligand, forming an inorganic layer that alternates along the c axis of the unit cell with bilayers, consisting of methyl groups and water of crystallization. The thermal variation of the magnetic susceptibility follows the Curie-Weiss law, with a large negative Weiss constant, theta = -60 K, indicating the presence of antiferromagnetic AF exchange interactions between neighboring Cr(II) ions. The magnetic behavior and the magnetic dimensionality have been analyzed in terms of Fisher's classical limiting form of the Heisenberg chain theory, and a value of J = -9.3 cm(-1) was found. The negative value of the intra-chain exchange constant coupling J confirms the presence of an AF coupling. No sign of long-range magnetic ordering down to 2 K (the lowest measured temperature) is observed, in agreement with the predominant one-dimensional character of the exchange interactions.

Synthesis, morphology, and magnetic characterization of iron oxide nanowires and nanotubes.

We have explored the synthesis of iron oxide particles, tubes, and fibrils within the pores of nanoporous polycarbonate and alumina membranes. The membranes contain uniformly distributed cylindrical pores with monodispersed diameters (varying between 20 and 200 nm) and thicknesses of 6 and 60 microm, respectively. By hydrolysis and polymerization of iron salts, particles of different sizes and phases were formed in the pores, building iron oxide particle nanowires. Alternatively, by the sol-gel technique, using as reagents metalloorganic compounds, fibrils and tubes of different iron oxide phases were prepared. Structural and morphological investigations performed using scanning electron microscopy and transmission electron microscopy revealed ordered iron oxide particle wires, tubes, and fibrils formed inside the membrane nanopores. Magnetic characterization was accomplished with a vibrating sample magnetometer. Below the blocking temperature (T(B)), the magnetic behavior of the nanowires was governed by dipolar interaction between nearest-neighbor nanoparticles inside the pore, whereas the energy barrier, and therefore the T(B) value, was mainly governed by dipolar interaction between magnetic moments over larger (interpore) distances. As expected, crystalline iron oxide nanotubes exhibited magnetic perpendicular anisotropy due to their magnetocrystalline and shape anisotropy.